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Title: Ultrasmall amorphous zirconia nanoparticles catalyse polyolefin hydrogenolysis
Abstract Carbon–carbon bond cleavage reactions, adapted to deconstruct aliphatic hydrocarbon polymers and recover the intrinsic energy and carbon value in plastic waste, have typically been catalysed by metal nanoparticles or air-sensitive organometallics. Metal oxides that serve as supports for these catalysts are typically considered to be inert. Here we show that Earth-abundant, non-reducible zirconia catalyses the hydrogenolysis of polyolefins with activity rivalling that of precious metal nanoparticles. To harness this unusual reactivity, our catalytic architecture localizes ultrasmall amorphous zirconia nanoparticles between two fused platelets of mesoporous silica. Macromolecules translocate from bulk through radial mesopores to the highly active zirconia particles, where the chains undergo selective hydrogenolytic cleavage into a narrow, C 18 -centred distribution. Calculations indicated that C–H bond heterolysis across a Zr–O bond of a Zr(O) 2 adatom model for unsaturated surface sites gives a zirconium hydrocarbyl, which cleaves a C–C bond via β-alkyl elimination.  more » « less
Award ID(s):
2108306
NSF-PAR ID:
10435102
Author(s) / Creator(s):
; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; more » ; ; ; ; ; « less
Date Published:
Journal Name:
Nature Catalysis
Volume:
6
Issue:
2
ISSN:
2520-1158
Page Range / eLocation ID:
161 to 173
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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